Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, ammonium salt thereof, and method for producing same

ABSTRACT

Provided are a water-soluble triarylphosphine for a palladium catalyst, which has high selectivity in a telomerization reaction and is easily recovered with efficiency, an ammonium salt thereof, and a method for efficiently producing the same. Specifically, provided are bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine; a bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammonium salt obtained by reacting the phosphine with a tertiary amine having a total of 3 to 27 carbon atoms in groups bonded to one nitrogen atom; and a method for producing the same.

TECHNICAL FIELD

The present invention relates tobis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, an ammonium saltthereof, and a method for producing the same.

BACKGROUND ART

A palladium catalyst comprised of a phosphorous compound and a palladiumcompound is useful as a catalyst for a telomerization reaction betweentwo conjugated alkadiene molecules and a nucleophilic reactant.Specifically, it is useful as a catalyst for production of2,7-octadien-1-ol by reacting two butadiene molecules with one watermolecule in the presence of carbon dioxide and a tertiary amine toperform a telomerization reaction. 7-Octenal can be derived from2,7-octadien-1-ol thus obtained by an isomerization reaction and1,9-nonanedial can be derived from 7-octenal by a hydroformylationreaction. From the viewpoint that 1,9-nonanediamine which is useful as araw material for a monomer for a polymer can be derived from1,9-nonanedial by a reductive amination reaction, the 2,7-octadien-1-olis of a high industrial value, and it is therefore important to developa catalyst advantageous for the production thereof.

In order to produce 2,7-octadien-1-ol in an industrially advantageousmanner, it is preferable to recover palladium as a noble metal in thetelomerization reaction and reuse it in the reaction. As such a methodfor producing 2,7-octadien-1-ol, there are two methods using atelomerization reaction, as followings:

(A) a method for producing 2,7-octadien-1-ol, in which butadiene andwater are subjected to a telomerization reaction in the presence of apalladium catalyst comprised of a palladium compound and a water-solublephosphine in an aqueous sulfolane solution including a carbonate of atertiary amine and a bicarbonate of a tertiary amine to generate2,7-octadien-1-ol, at least part of the reaction mixed liquid isextracted with a saturated aliphatic hydrocarbon or the like to separatethe 2,7-octadien-1-ol by extraction, and at least a part of thesulfolane eluent including the palladium catalyst is recycled and usedin the reaction (see PTLs 1 to 3), and

(B) a method for producing 2,7-octadien-1-ol, in which a tertiary aminehaving a function as a surfactant capable of compensating for a lowreaction rate due to low solubility of butadiene in water coexiststherewith in a two-phase system including an aqueous phase having apalladium catalyst comprised of a palladium compound and a water-solublephosphorus-containing compound dissolved in water and an organic phasewhich is butadiene, and then butadiene and water are subjected to atelomerization reaction (see PTL 4 and NPL 1).

In the method (A), 2,7-octadien-1-ol is extracted by adding a saturatedaliphatic hydrocarbon to a telomerization reaction liquid, and it isthus necessary to install equipment for distillation and recovery of thesaturated aliphatic hydrocarbon, which results in an increase in costburden associated with the equipment. Further, sulfolane is moreexpensive than ordinary hydrocarbon-based solvents, such as hexane, andaccordingly, it is necessary to recover the sulfolane by subjecting the2,7-octadien-1-ol phase obtained by extraction to washing with water, orthe like. In addition, since sulfolane is a sulphur atom-containingsubstance, in a case of incineration disposal of sulfolane, anincinerator having desulphurization equipment is required. Therefore,there is a demand for a method for conveniently recovering most of apalladium catalyst after a telomerization reaction while not usingsulfolane in the telomerization reaction.

In the method (B), dimethyldodecylamine, for example, is used as atertiary amine. Since the dimethyldodecylamine has a function as asurfactant, complicated operations such as multiple extraction andrecovery, or distillation and separation are required so as to increasethe recovery of a tertiary amine. Further, according to Examples, it canbe said that the method (B) is a method having low selectivity for2,7-octadien-1-ol. Therefore, there is also a demand for a method inwhich the tertiary amine to be easily recovered can be used, and theselectivity for 2,7-octadien-1-ol is high.

Moreover, as a method for producing a water-soluble triarylphosphinewhich can be used in a telomerization reaction, the following methodsare known:

(1) a method for producing a bis(3-sulphonatophenyl)phenylphosphinedisodium salt, by dissolving triphenylphosphine in sulphuric acid, andthen reacting the solution with sulphur trioxide in fuming sulphuricacid (see NPLs 2 and 3),

(2) a method for producing a bis(3-sulphonatophenyl)phenylphosphinedisodium salt by sulphonation of triphenylphosphine using an anhydrousmixture of sulphuric acid and orthoboric acid (see PTL 5),

(3) a method in which triarylphosphine having an electron donating groupsuch as a methyl group and a methoxy group in an aromatic ring isreacted with sulphur trioxide in the presence of sulphuric acid (see NPL4), and

(4) a method in which triarylphosphine having an electron donating groupsuch as a methyl group and a methoxy group in each of three aromaticrings is reacted with sulphur trioxide in the presence of sulphuric acid(see NPL 5).

In the case of using the alkali metal salt of a triarylphosphine havinga sulphonate group, obtained by these methods, in a telomerizationreaction, there is a problem in that inorganic salts such as hydrogencarbonate of an alkali metal are accumulated in the reaction system,thus blocking pipes. It is known that as a method to avoid this problem,it is preferable to use an ammonium salt obtained by reacting atriarylphosphine having a sulphonate group with a tertiary amine as acatalyst for a telomerization reaction (see PTL 6).

In the method (1) for producing a water-soluble triarylphosphine, abis(3-sulphonatophenyl)phenylphosphine disodium salt can be produced bysulphonating triphenylphosphine having a benzene ring as an equivalentaromatic ring relative to one phosphorus atom, bonded thereto withsulphur trioxide, followed by neutralization with sodium hydroxide, butthe yield is as low as 60%. This is mainly caused by by-production of atris(3-sulphonatophenyl)phosphine trisodium salt, indicating that it isdifficult to selectively introduce only “two” sulpho groups with respectto the equivalent aromatic ring.

The method (2) for producing a water-soluble triarylphosphine is amethod in which orthoboric acid is used instead of sulphur trioxideduring a sulphonation reaction. Thebis(3-sulphonatophenyl)phenylphosphine disodium salt is acquired with ayield of 94%, but in order to remove boric acid completely, toluene andtriisooctylamine are added to a sulphonation reaction liquid once tocause a desired amine salt to be present in an organic phase, theorganic phase is sufficiently washed with water, and the aqueous phaseobtained by adding an aqueous sodium hydroxide solution to the washedorganic phase is neutralized with sulphuric acid, and then concentrated.Then, methanol is added thereto to obtain a supernatant, from whichmethanol is removed, thereby acquiring abis(3-sulphonatophenyl)phenylphosphine disodium salt. Although the yieldis high, it is necessary to repeat washing to remove boric acid.Therefore, this method is difficult to carry out industrially.

The method (3) for producing a water-soluble triarylphosphine is amethod in which a triarylphosphine in which an electron donating groupsuch as a methyl group and a methoxy group is introduced in advance toan aromatic ring is reacted with sulphur trioxide in the presence ofsulphuric acid. The method simply shows that only in the case where atriarylphosphine having a non-equivalent aromatic ring such asbis(4-methoxyphenyl)phenylphosphine or the like is used as a rawmaterial, the number of the introduced sulpho groups of thebis(4-methoxy-3-sulphonatophenyl)phenylphosphine disodium salt or thelike can be controlled, but does not show that the number of theintroduced sulpho groups in tris(2-methylphenyl)phosphine having anequivalent aromatic ring can be controlled.

The method (4) for producing a water-soluble triarylphosphine shows thata bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine disodiumsalt can be acquired, but does not disclose specific production methodsand yields thereof, which means the method simply shows the probabilityof isolating the present compound.

As a method for producing an ammonium salt of a triarylphosphine havinga sulphonate group, methods in which an alkali metal salt of atriarylphosphine having a sulphonate group is used as a raw material, acounter-cation is converted into a desired ammonium salt by an ionexchange process in the following manner are known. The methods are asfollows:

a method in which sulphuric acid is added to an aqueous solution of adiphenyl(3-sulphonatophenyl)phosphine sodium salt, 4-methyl-2-pentanoneis then added thereto, and triethylamine is added to the obtainedorganic phase, thereby precipitating a solid-statediphenyl(3-sulphonatophenyl)phosphine triethylammonium salt (see PTL 6);and

a method in which a diphenyl(3-sulphonatophenyl)phosphine sodium salt ispressurized with carbon dioxide in the presence of triethylamine,ethanol, and 2-propanol, and a desired product is acquired from afiltrate of the reaction liquid (see PTL 7).

CITATION LIST Patent Literature

[PTL 1] JP-A-64-25739

[PTL 2] JP-A-3-232831

[PTL 3] JP-A-6-321828

[PTL 4] JP-T-8-501800

[PTL 5] JP-A-8-176167

[PTL 6] JP-A-2002-371088

[PTL 7] JP-A-2003-171388

Non Patent Literature

[NPL 1] Journal of Molecular Catalysis A: Chemical, vol. 97, 1995, pp.29 to 33

[NPL 2] Tetrahedron Letters, 2000, vol. 41, pp. 4503 to 4505

[NPL 3] Organic Process Research & Development, 2000, vol. 4, pp. 342 to345

[NPL 4] Tetrahedron Letters, vol. 43, 2002, pp. 2543 to 2546

[NPL 5] Advanced Synthesis & Catalysis, 2008, vol. 350, pp. 609 to 618

SUMMARY OF INVENTION Technical Problem

In the ion exchange method described in PTL 6, according to theinvestigations of the present inventors,bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine was insufficientlyextracted with an acyclic ketone solvent, and therefore, the yield wasas low as 30% or less.

In the ion exchange method described in PTL 7, according to theinvestigations of the present inventors, when the same operation wascarried out using abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine disodium salt,the ion exchange rate of the counter-cation was as low as 20% or less.

Therefore, it is an object of the present invention to provide awater-soluble triarylphosphine for a palladium catalyst, which has highselectivity in a telomerization reaction and is easily recovered withefficiency, and a method for producing the same efficiently.

Solution to Problem

The present inventors have conducted extensive studies, and as a result,they have found that the selectivity for desired products is increasedin a telomerization reaction of two molecules of an alkadiene such asbutadiene with a nucleophilic reactant such as water by using apalladium catalyst comprised of a specific ammonium salt ofbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine and a palladiumcompound. Further, they have also found that in the case of using thepalladium catalyst in a telomerization reaction, products can beextracted from the organic phase by adding an organic solvent having aspecific dielectric constant to the obtained telomerization reactionliquid, while recovery of the palladium catalyst from the aqueous phasecan be carried out with high yield, thereby completing the presentinvention.

That is, the present invention relates to [1] to [7] below.

[1] Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine.

[2] A bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinediammonium salt obtained by reacting thebis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine according to [1]with a tertiary amine having a total of 3 to 27 carbon atoms in groupsbonded to one nitrogen atom.

[3] The bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinediammonium salt according to [2], wherein the tertiary amine istrimethylamine, triethylamine, tripropylamine, triisopropylamine,tributylamine, triisobutylamine, tri-s-butylamine, tri-t-butylamine,tripentylamine, triisopentylamine, trineopentylamine, trihexylamine,triheptylamine, trioctylamine, triphenylamine, tribenzylamine,N,N-dimethylethylamine, N,N-dimethylpropylamine,N,N-dimethylisopropylamine, N,N-dimethylbutylamine,N,N-dimethylisobutylamine, N,N-dimethyl-s-butylamine,N,N-dimethyl-t-butylamine, N,N-dimethylpentylamine,N,N-dimethylisopentylamine, N,N-dimethylneopentylamine,N,N-dimethylhexylamine, N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine,N,N-dimethylundecylamine, N,N-dimethyldodecylamine,N,N-dimethylphenylamine, N,N-dimethylbenzylamine,N,N-diethylmonomethylamine, N,N-dipropylmonomethylamine,N,N-diisopropylmonomethylamine, N,N-dibutylmonomethylamine,N,N-diisobutylmonomethylamine, N,N-di-s-butylmonomethylamine,N,N-di-t-butylmonomethylamine, N,N-dipentylmonomethylamine,N,N-diisopentylmonomethylamine, N,N-dineopentylmonomethylamine,N,N-dihexylmonomethylamine, N,N-diheptylmonomethylamine,N,N-dioctylmonomethylamine, N,N-dinonylmonomethylamine,N,N-didecylmonomethylamine, N,N-diundecylmonomethylamine,N,N-didodecylmonomethylamine, N,N-diphenylmonomethylamine,N,N-dibenzylmonomethylamine, N,N-dipropylmonomethylamine,N,N-diisopropylmonoethylamine, N,N-dibutylmonoethylamine,N,N-diisobutylmonoethylamine, N,N-di-s-butylmonoethylamine,N,N-di-t-butylmonoethylamine, N,N-dipentylmonoethylamine,N,N-diisopentylmonoethylamine, N,N-dineopentylmonoethylamine,N,N-dihexylmonoethylamine, N,N-diheptylmonoethylamine,N,N-dioctylmonoethylamine, N,N-dinonylmonoethylamine,N,N-didecylmonoethylamine, N,N-diundecylmonoethylamine,N,N-didodecylmonoethylamine, N,N-diphenylmonoethylamine,N,N-dibenzylmonoethylamine, or trinonylamine.

[4] A mixture comprising 5% by mole or less ofbis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% by mole ormore of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, and 15%by mole or less of tris(6-methyl-3-sulphophenyl)phosphine.

A mixture containing 80% by mole or more of abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt obtained by reacting the mixture according to [4] with a tertiaryamine having a total of 3 to 27 carbon atoms in groups bonded to onenitrogen atom.

[6] A method for producing bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, having; a step ofreacting 2.5 moles to 4.5 moles of sulphur trioxide with 1 mole oftris(2-methylphenyl)phosphine in the presence of concentrated sulphuricacid to obtain a sulphonation reaction liquid, and diluting the obtainedsulphonation reaction liquid with water to obtain a diluted liquid; astep of neutralizing the diluted liquid with an alkali metal hydroxide;and a step of bringing the aqueous solution obtained in theneutralization step into contact with a strongly acidic cation exchangeresin.

[7] A method for producing abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt by reacting bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphinewith a tertiary amine having a total of 3 to 27 carbon atoms in groupsbonded to one nitrogen atom.

Advantageous Effects of Invention

According to the present invention, high selectivity in a telomerizationreaction can be accomplished by using a water-soluble triarylphosphinefor a palladium catalyst, and the palladium catalyst after use can beefficiently recovered. Further, a water-soluble triarylphosphine, whichwill be a raw material for a palladium catalyst, can be selectivelyproduced by the production method of the present invention.

DESCRIPTION OF EMBODIMENTS

First, in the present specification, the restrictive wording with “beingpreferable” can be arbitrarily adopted, and a combination of restrictivewordings with “being preferable” can be said to be more preferred.

The present invention providesbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine and an ammoniumsalt thereof. The ammonium salt thereof is more specifically abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt.

These can be produced efficiently by the following steps, but theinvention is not particularly limited to the following steps.

[1. Sulphonation Step]

A step of reacting 2.5 moles to 4.5 moles of sulphur trioxide with 1mole of tris(2-methylphenyl)phosphine in the presence of concentratedsulphuric acid to obtain a sulphonation reaction liquid, and dilutingthe obtained sulphonation reaction liquid with water to obtain a dilutedliquid is included.

[2. Neutralization Step]

A step of neutralizing the diluted liquid with an alkali metal hydroxideto obtain an aqueous solution including abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phsphine dialkali metalsalt.

[3. Ion Exchange Step]

A step of bringing the aqueous solution obtained in the neutralizationstep into contact with a strongly acidic cation exchange resin to formbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine.

The bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine can beproduced by the steps hitherto described. Further, for the production ofa bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt, the following steps are further required.

[4. Ammonium Salt Forming Step]

A step of reacting bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphinewith a tertiary amine having a total of 3 to 27 carbon atoms in groupsbonded to one nitrogen atom to form abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt.

Furthermore, the steps will be described in detail below, but from theviewpoint that the phosphine compound is easily oxidized by oxygen,although not being clearly described, operations in the steps arecarried out in an inert gas atmosphere in principle. Furthermore, fromthe same viewpoint, in the case of using a solvent, it is preferable touse a solvent having dissolved oxygen included in the solvent is purgedwith an inert gas. Examples of the inert gas include nitrogen, helium,and argon, and from the viewpoint of high industrial availability, it ispreferable to use nitrogen gases.

[1. Sulphonation Step]

The method for producing tris(2-methylphenyl)phosphine is notparticularly limited, and the tris(2-methylphenyl)phosphine can beproduced according to a known method. For example, a reaction ofphosphorous trichloride with a Grignard reagent obtained from2-bromotoluene (see Journal of Organic Chemistry, 1978, vol. 43, pp.2941 to 2956) and the like are known.

Furthermore, as the tris(2-methylphenyl)phosphine, those that arecommercially distributed can be used, and for example, “TOTP”(registered trademark) manufactured by Hokko Chemical Industry Co.,Ltd., and the like can be purchased and used.

The operation sequence in the reaction of tris(2-methylphenyl)phosphinewith sulphur trioxide in the presence of concentrated sulphuric acid isnot particularly limited, but for example, tris(2-methylphenyl)phosphinecan be sulphonated by dissolving tris(2-methylphenyl)phosphine inconcentrated sulphuric acid, followed by reaction with sulphur trioxide.

Furthermore, sulphonation can also be carried out by the reaction withorthoboric acid instead of sulphur trioxide. According to the findingsof the present inventors, in the case of using orthoboric acid, from theviewpoint that the removal of orthoboric acid from the sulphonationreaction liquid is complicated, it is preferable to use sulphurtrioxide, and it is more preferable to use fuming sulphuric acidincluding sulphur trioxide and sulphuric acid.

The sulphonation step can be carried out using a continuous stirred tankreactor equipped with a jacket. The continuous stirred tank reactor asmentioned herein is a reactor designed such that raw materials suppliedto the reactor are mixed in a substantially homogeneous dispersion statewithout any delay.

The material for the reactor is preferably stainless steel, Hastelloy C,titanium, or the like, and further, as a material for an inner wall of areactor, a glass-lined material may be used. From the viewpoint ofavoiding the incorporation of metal ions originating from the reactorinto a desired product, it is preferable to use glass-lined material forthe inner wall. Further, the glass lining process is a method in whichtwo materials, a metal and glass, are fused to perform surfacemodification of the metal.

The sulphonation step can be carried out in any of a batch mode(including a semi-continuous mode) and a flow and continuous mode. Insome cases, it can also be carried out in a flow and continuous mode byconnecting two or three continuous stirred tank reactors in series. Fromthe viewpoint that simplification of equipment results from dilution ofa sulphonation reaction liquid with water as described later and thesubsequent neutralization step, both carried out in one reaction tank,it is preferable to carry out the process in a batch mode (including asemi-continuous mode).

Concentrated sulphuric acid serves to dissolvetris(2-methylphenyl)phosphine. As the concentrated sulphuric acid, onehaving a high content of sulphuric acid is preferred, and from theviewpoint of industrial availability, one having a concentration of 96%by mass or more is more preferably used. A higher content of sulphuricacid in concentrated sulphuric acid is preferable since it can inhibitthe hydrolysis of sulphur trioxide in fuming sulphuric acid. From theviewpoint that fuming sulphuric acid is more expensive than sulphuricacid, it is economically preferable to inhibit the hydrolysis of sulphurtrioxide.

Since concentrated sulphuric acid used for sulphonation is generallysubjected to a disposal treatment by forming a sulphuric acid alkalimetal salt by neutralization with an alkali metal hydroxide or the like,production conditions for reducing the amount of sulphuric acid used arepreferred. From this viewpoint, the amount of sulphuric acid used ispreferably about an amount which allows tris(2-methylphenyl)phosphine tobe dissolved, and more preferably an amount which adjusts the amount oftris(2-methylphenyl)phosphine to be from 20% by mass to 70% by mass.Within this range, the amount of sulphuric acid to be disposed of can bereduced, it becomes possible to perform a reaction with sulphur trioxidein a sufficiently mixed state due to low viscosity of the prepared mixedsolution, and in addition, the yield of the desired product is enhanced.

The temperature at a time of preparation of a concentrated sulphuricacid solution of tris(2-methylphenyl)phosphine is preferably from 0° C.to 100° C., and more preferably from 20° C. to 40° C. Within this range,the oxidation reaction of tris(2-methylphenyl)phosphine does notproceed, it becomes possible to perform a reaction with sulphur trioxidein a sufficiently mixed state due to low viscosity of the prepared mixedsolution, and in addition, the yield of the desired product is enhanced.

Sulfur trioxide is preferably used for the reaction in the form of afuming sulphuric acid in which sulphur trioxide is dissolved insulphuric acid. The concentration of sulphur trioxide in fumingsulphuric acid is preferably from 10% by mass to 60% by mass, and morepreferably from 20% by mass to 50% by mass. Within this range, theamount of sulphuric acid practically used can be reduced, and the timerequired for the sulphonation step can be shortened due to a fact thatthe sulphur trioxide concentration in the reaction system can bemaintained at a certain level or higher.

The amount of sulphur trioxide used is preferably from 2.5 moles to 4.5moles, and more preferably from 3.0 moles to 4.0 moles, with respect toone mole of phosphorous atoms contained intris(2-methylphenyl)phosphine. Within this range, the yield of thedesired product is high. Further, the numerical value range is anumerical value not considering the consumption by hydrolysis. In thecase where consumption by hydrolysis is considered, it is preferable toincrease the amount of sulphur trioxide used according to the amount.

The reaction temperature for the sulphonation step is preferably from 0°C. to 100° C., more preferably from 10° C. to 50° C., and still morepreferably from 20° C. to 50° C. Within this range, even in the statewhere the reaction time is short, the yield of a desired product ishigh.

It is preferable to add fuming sulphuric acid to a concentratedsulphuric acid solution of tris(2-methylphenyl)phosphine slowly, and thetime taken for the addition is preferably from 0.25 hours to 5 hours,and more preferably from 0.5 hours to 3 hours. Within this range, thereaction time is not too long, and the yield of a desired product ishigh. Further, it is preferable that after the addition of fumingsulphuric acid, the flow path of the fuming sulphuric acid is washedwith concentrated sulphuric acid, and a washing liquid thus obtained ismixed with the reaction solution.

The reaction time after the completion of addition of fuming sulphuricacid is preferably from 2 hours to 20 hours, and more preferably from 2hours to 8 hours. In the case of this range, the yield of a desiredproduct is high.

(Water Dilution Operation)

Unreacted sulphur trioxide can be hydrolyzed by diluting thesulphonation reaction liquid obtained by the operation above with water,whereby it is possible to stop the sulphonation reaction.

Furthermore, water used for the dilution serves to remove the dilutionheat of concentrated sulphuric acid and the hydrolysis reaction heat ofsulphur trioxide, and also serves as a solvent in the neutralizationstep of the next step.

The temperature of water used for dilution may be any temperature atwhich water does not freeze, and it is preferably from 1° C. to 40° C.,and more preferably from 2° C. to 25° C. Among the temperatures in thisrange, a lower temperature is preferred since heat can be efficientlyremoved.

The amount of water used may be at least any amount in which unreactedsulphur trioxide can be hydrolyzed, but from the viewpoint of control ofthe temperature in the neutralization step as described later, it isfrom 1 time to 20 times by mass that of the sulphonation reactionliquid. Within this range, heat removal is easy and the amount of wastewater in the neutralization step as described later can be reduced.

The liquid temperature at the time of dilution with water is preferablyfrom 0° C. to 100° C., and more preferably from 1° C. to 40° C. Withinthis range, operations such as lowering the temperature of the liquid ata time of starting the neutralization step are not required, and thus,the productivity can be improved.

[2. Neutralization Step]

In the neutralization step, the reactor used in the sulphonation step isused as it is, and further, it is preferable to continuously carry outthe step in a batch mode (including a semi-continuous mode) from theviewpoint of simplification of equipment.

Examples of the alkali metal hydroxide used in the neutralization stepinclude lithium hydroxide, sodium hydroxide, and potassium hydroxide.Among these, potassium hydroxide and sodium hydroxide are preferred, andsodium hydroxide is more preferred.

By using the alkali metal hydroxide, a high ion exchange rate frombis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali metalsalt to bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine with astrongly acidic cation exchange resin can be accomplished.

The alkali metal hydroxide may be used in the form of a solid and may beused as an aqueous solution. However, from the viewpoints of avoidinglocal heat generation at a time of neutralization and increasing theheat removal efficiency, the alkali metal hydroxide is preferably usedas an aqueous solution. The concentration of the aqueous alkali metalhydroxide solution is not particularly limited, and the aqueous alkalimetal hydroxide solution is preferably used at a concentration of 10% bymass to 50% by mass, and more preferably used at a concentration of 20%by mass to 40% by mass. Within this range, the liquid amount after theneutralization is low, and thus, the amount of waste water can bereduced. Further, it is preferable that the aqueous alkali metalhydroxide solution is slowly added to the sulphonation reaction liquidobtained in the sulphonation step, and in some cases, the aqueous alkalimetal hydroxide solution can be added in several separate portions.Further, after using the aqueous alkali metal hydroxide solution in theconcentration range, aqueous alkali metal hydroxide solutions havingdifferent concentrations, for example, an aqueous alkali metal hydroxidesolution (usually an aqueous alkali metal hydroxide solution having alow concentration) having a concentration out of the range may be usedlater.

The amount of alkali metal hydroxide used is not particularly limited aslong as it can neutralize sulphuric acid andbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, and it ispreferably an amount such that the pH of the aqueous solution at 25° C.after the completion of neutralization is preferably from 7.0 to 9.5,and more preferably from 7.5 to 8.5. Within this range, most ofsulphuric acid can be induced to a sulphuric acid alkali metal salt.Further, excess alkali metal hydroxide can be converted to water in theion exchange step as described later.

The neutralization temperature is not particularly limited, and usually,it is preferably from 0° C. to 40° C., and more preferably from 1° C. to25° C. in order to promote desirable precipitation of alkali metalsulphate. When the neutralization temperature is 0° C. or higher, theamount of energy consumed, relevant to cooling, can be reduced, which isthus preferable. Further, when the neutralization temperature is 40° C.or lower, precipitation of the alkali metal sulphate during thetransportation of the liquid can be inhibited, and therefore, there isno concern about pipes becoming blocked.

The time required for the neutralization is any time as long as it is ina range suitable for the heat removal ability of a reactor used.Specifically, the time is preferably from 0.5 hours to 20 hours, andmore preferably from 2 hours to 5 hours. When the time is 0.5 hours orlonger, it is possible to remove neutralization heat efficiently. As aresult, it is economically advantageous since it is not necessary to usea continuous stirred tank with high efficiency in heat removal. When thetime is 20 hours or shorter, the increase in the amount of energyconsumed for maintenance of the set temperature can be inhibited, whichis thus preferable.

The aqueous solution formed by the neutralization in the present step(hereinafter referred to as a neutralized liquid) has abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali metalsalt and an alkali metal sulphate as a main component.

The solubility in an alcohol, such as methanol, ethanol, and 1-propanol,of the bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedialkali metal salt is higher than that of the alkali metal sulphate,and thus, by using the difference in solubility, the alkali metalsulphate can be separated out. Although it is possible to precipitatethe alkali metal sulphate by directly adding an alcohol to theneutralized liquid, it is preferable to evaporate as much water aspossible from the neutralized liquid in advance, and it is morepreferable to evaporate 90% by mass to 98% by mass of the water in theneutralized liquid, from the viewpoints of reducing the amount ofalcohol used and inhibiting the incorporation of the alkali metalsulphate into a desired product. In this manner, an approach in whichthe alcohol is added to a concentrate obtained by evaporating water toseparate out the alkali metal sulphate is preferred.

Examples of the alcohol include methanol, ethanol, and 1-propanol, andfrom the viewpoint of reducing the amount of the alcohol, it ispreferable to use methanol.

The amount of the alcohol used for the separation of the alkali metalsulphate is not particularly limited, and is preferably from 0.5-fold bymass to 80-fold by mass, and more preferably from 5-fold by mass to20-fold by mass, with respect to the concentrate. Within this range, ata time of isolation of a desired product, the amount of alcoholevaporated can be reduced, and further, the alkali metal salt can besufficiently precipitated.

An insoluble material of the alcohol solution is the alkali metalsulphate, which may be separated and removed by filtration ordecantation. The temperature for filtration or decantation is preferablyfrom 0° C. to 50° C., and more preferably from 1° C. to 25° C. Withinthis range, it is possible to precipitate only the alkali metal sulphateselectively, and thus, the yield of a desired product is high.

In the case where the alkali metal sulphate is incorporated into thealcohol solution obtained as described above, the obtained alcoholsolution may be concentrated and be dissolved in an alcohol again torepeat the operation for separation and removal of the alkali metalsulphate.

By evaporating the alcohol from the alcohol solution, it is possible toacquire a mixture of 5% by mole or less of abis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine alkali metalsalt, 80% by mole or more of abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali metalsalt, and 15% by mole or less of atris(6-methyl-3-sulphonatophenyl)phosphine trialkali metal salt as asolid. This mixture will be hereinafter abbreviated as a mixture ofalkali metal salts.

In order to increase the content of thebis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali metalsalt in the mixture of alkali metal salts, column chromatography using amixed solvent including water, tetrahydrofuran, and the like as a mobilephase, which is passed through columns packed with silica gel, can beused. Alternatively, a method in which an aqueous solution of a mixtureof alkali metal salts is prepared and washed with an organic solventsuch as 2-butanone can also be used.

[3. Ion Exchange Step]

By reacting the mixture of alkali metal salts obtained in theneutralization step with a strongly acidic cation exchange resin,bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine can be derivedfrom the bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedialkali metal salt.

According to the investigations of the present inventors, in a knownmethod including reacting a triarylphosphine in which a counter-cationof a sulpho group is an alkali metal with a tertiary amine and carbondioxide in the presence of an alcohol solvent, and a known methodincluding reacting a triarylphosphine in which a counter-cation of asulpho group is an alkali metal with a protonic acid in a solvent suchas an acyclic ketone, the yield of a desired product is lowered in anycase. Therefore, it is crucial to use a strongly acidic ion exchangeresin, and according to the method, the yield of a desired product isincreased.

It is also possible to bring an alcohol solution of the mixture ofalkali metal salts as it is into contact with a strongly acidic cationexchange resin, but since the solubility of the mixture of alkali metalsalts in an alcohol is lower than that in water, it is preferable tobring the mixture of alkali metal salts from an aqueous solution intocontact with a strongly acidic cation exchange resin to undergo areaction.

By using a strongly acidic cation exchange resin as a cation exchangeresin, the alkali metal ions can be sufficiently converted to protonseven with a small amount of the ion exchange resin.

As the strongly acidic cation exchange resin, those in which a sulphogroup is introduced to a copolymer of styrene and divinylbenzene, acopolymer of perfluorosulphonic acid and tetrafluoroethylene, and thelike can be preferably used.

Examples of the strongly acidic cation exchange resin include thosewhich are non-aqueous and aqueous, either of which may be used.According to the kind of a substrate, a macroporous type substrate, agel type substrate, and the like can be mentioned, either of which maybe used. As the strongly acidic cation exchange resin, those in whichthe counterion of a sulpho group contained in the resin is a proton or asodium ion are generally known. In the case where the counterion is asodium ion, the sodium ion is converted into a proton by carrying out apre-treatment with a protonic acid such as hydrochloric acid andsulphuric acid, then the pretreated resin is used. In the case of aresin in which the counterion is a proton, it can be used without apre-treatment.

The strongly acidic cation exchange resin may have a powder shape orparticulate shape, but from the viewpoint of avoiding damage due tofriction in the state of use, it is preferable to use a resin having aparticulate shape. In the case of using a resin having a particulateshape, the average particle diameter is not particularly limited, and ispreferably from 0.3 mm to 3 mm, and more preferably from 0.5 mm to 1.5mm. When the average particle diameter is 0.3 mm or more, it isdifficult for the resin to be incorporated into a product, whereas whenthe average particle diameter is 3 mm or less, a large contact area ofthe resin with the aqueous solution of the mixture of alkali metal saltscan be maintained, and as a result, the amount of the strongly acidiccation exchange resin used can be reduced.

Examples of the strongly acidic cation exchange resin formed byintroducing a sulpho group into a copolymer of styrene anddivinylbenzene, which satisfies the above, include Amberlyst 15,Amberlyst 16, Amberlyst 31, Amberlyst 32, and Amberlyst 35[in whichAmberlyst is a registered trademark], all manufactured by Rohm and HaasCompany, Dowex 50W, Dowex 88, and Dowex G-26 [in which Dowex is aregistered trademark], all manufactured by Dow Chemical Company, andDiaion SK104, Diaion SK1B, Diaion PK212, Diaion PK216, and Diaion PK228[in which Diaion is a registered trademark], all manufactured byMitsubishi Chemical Corporation.

Examples of the strongly acidic cation exchange resin as a copolymer ofperfluorosulphonic acid and tetrafluoroethylene include Nafion SAC-13and Nafion NR-50 [in which Nafion is a registered trademark], bothmanufactured by E. I. du Pont de Nemours and Company.

The strongly acidic cation exchange resins may be used alone or incombination of two or more kinds thereof.

The ion exchange step can be carried out in either a flow mode or abatch mode. In the case of carrying out in a flow mode using a column, afixed bed reactor, or the like, damage due to the friction of thestrongly acidic cation exchange resin can be inhibited, and further,there is an effect that the equilibrium reaction is biased, whereby theamount of the strongly acidic cation exchange resin used can be reduced.

From the viewpoint of making the flow of the aqueous solution uniform,it is preferable that the reactor has a tubular structure. The tubediameter is not particularly limited, but it is preferably from 50 mm to500 mm from the viewpoint of making the exchange operation of thestrongly acidic cation exchange resin convenient. The length and numberof the reactor tube as a reactor are not particularly limited, but arepreferably appropriately set from the viewpoint of the production cost,strongly acidic cation exchange resin and the like, which the resin isrequired to achieve a desired production capacity of the reactor.

In addition, the laminar flow may be in a down-flow mode for supplyingthe aqueous solution from the top of a reactor or an upflow mode forsupplying from the bottom of a reactor when the reactor is a fixed bedreactor.

The concentration of the mixture of alkali metal salts in the aqueoussolution of the mixture of alkali metal salts is preferably from 1% bymass to 30% by mass, and more preferably from 5% by mass to 20% by mass.Within these ranges, it is possible to convert 99% by mole or more ofthe alkali metal ions into protons even with a small amount of waterused.

The temperature of the aqueous solution of the mixture of alkali metalsalts is preferably from 10° C. to 120° C., and more preferably from 15°C. to 40° C. If the temperature is 10° C. or higher, there is noreduction in the ion exchange rate, and the increase in the amount ofthe strongly acidic cation exchange resin used can be avoided. Further,if the temperature is 120° C. or lower, the pores of the resin can beinhibited from being closed by the deformation of the ion exchangeresin, and in addition, the reduction in the rate of ion exchange can beinhibited.

The amount of the strongly acidic cation exchange resin used preferablycorresponds to 1.5 times or more the theoretical ion-exchangeable amountwhich is calculated from the amount of the alkali metal ions to bepreliminarily exchanged. By this, it is possible to exchange 99% by moleor more of the alkali metal ions included in the mixture of alkali metalsalts with protons. In addition, in the case where a higher ion exchangerate is desired, the alkali metal ions may undergo a reaction repeatedlywith the strongly acidic cation exchange resins.

The flow rate of the aqueous solution of the mixture of alkali metalsalts is not particularly limited, but the liquid hourly space velocity(LHSV), a value obtained by dividing a volume velocity (m³/hr) of theaqueous solution supplied by a volume (m³) of a resin layer includingthe strongly acidic cation exchange resin, is preferably from 5 hr⁻¹ to30 hr⁻¹, and more preferably from 10 hr⁻¹ to 20 hr⁻¹. Within this range,the ion exchange efficiency is high.

By evaporating water from an aqueous solution which has been broughtinto contact with the strongly acidic cation exchange resin, it ispossible to acquire a mixture of 5% by mole or less ofbis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% by mole ormore of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, and 15%by mole or less of tris(6-methyl-3-sulphophenyl)phosphine, as a solid.This mixture will be hereinafter abbreviated as an ion exchangedmixture.

[4. Ammonium Salt Forming Step]

It is possible to derive a corresponding ammonium salt by allowing asulpho group included in the ion exchanged mixture obtained in the ionexchange step to undergo a reaction with the same number of moles of atertiary amine.

It is preferable that the ion exchanged mixture is dissolved in water,and from the viewpoint of reducing the amount of the solvent evaporated,the ion exchanged mixture is preferably used as an aqueous solutionincluding 3% by mass to 25% by mass of the ion exchanged mixture.

The appropriate amount of the tertiary amine can be confirmed bypotentiometric titration. In the case of adding excess tertiary amine,the excess tertiary amine may be evaporated.

The amount of tertiary amine used is preferably 1-fold by mole to 3-foldby mole, more preferably 1.1-fold by mole to 2-fold by mole, and stillmore preferably 1.1-fold by mole to 1.5-fold by mole of that of thesulpho groups included in the ion exchanged mixture.

By concentrating a solution obtained by reacting the ion exchangedmixture with the tertiary amine to dryness, a desired product as a solidcan be isolated, and by evaporating a part of the water, a concentratedaqueous solution can be acquired or the solution may be used as it is.

By directly adding the tertiary amine to the aqueous solution of the ionexchanged mixture, and sufficiently mixing them at 10° C. to 30° C. over0.5 hours to 3 hours, the reaction with the corresponding ammoniumsufficiently proceeds.

Furthermore, as the tertiary amine, a tertiary amine having a total of 3to 27 carbon atoms in alkyl groups bonded to one nitrogen atom is used.

Examples of the tertiary amine include trimethylamine, triethylamine,tripropylamine, triisopropylamine, tributylamine, triisobutylamine,tri-s-butylamine, tri-t-butylamine, tripentylamine, triisopentylamine,trineopentylamine, trihexylamine, triheptylamine, trioctylamine,triphenylamine, tribenzylamine, N,N-dimethylethylamine,N,N-dimethylpropylamine, N,N-dimethylisopropylamine,N,N-dimethylbutylamine, N,N-dimethylisobutylamine,N,N-dimethyl-s-butylamine, N,N-dimethyl-t-butylamine,N,N-dimethylpentylamine, N,N-dimethylisopentylamine,N,N-dimethylneopentylamine, N,N-dimethylhexylamine,N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine,N,N-dimethyldecylamine, N,N-dimethylundecylamine,N,N-dimethyldodecylamine, N,N-dimethylphenylamine,N,N-dimethylbenzylamine, N,N-diethylmonomethylamine,N,N-dipropylmonomethylamine, N,N-diisopropylmonomethylamine,N,N-dibutylmonomethylamine, N,N-diisobutylmonomethylamine,N,N-di-s-butylmonomethylamine, N,N-di-t-butylmonomethylamine,N,N-dipentylmonomethylamine, N,N-diisopentylmonomethylamine,N,N-dineopentylmonomethylamine, N,N-dihexylmonomethylamine,N,N-diheptylmonomethylamine, N,N-dioctylmonomethylamine,N,N-dinonylmonomethylamine, N,N-didecylmonomethylamine,N,N-diundecylmonomethylamine, N,N-didodecylmonomethylamine,N,N-diphenylmonomethylamine, N,N-dibenzylmonomethylamine,N,N-dipropylmonomethylamine, N,N-diisopropylmonoethylamine,N,N-dibutylmonoethylamine, N,N-diisobutylmonoethylamine,N,N-di-s-butylmonoethylamine, N,N-di-t-butylmonoethylamine,N,N-dipentylmonoethylamine, N,N-diisopentylmonoethylamine,N,N-dineopentylmonoethylamine, N,N-dihexylmonoethylamine,N,N-diheptylmonoethylamine, N,N-dioctylmonoethylamine,N,N-dinonylmonoethylamine, N,N-didecylmonoethylamine,N,N-diundecylmonoethylamine, N,N-didodecylmonoethylamine,N,N-diphenylmonoethylamine, N,N-dibenzylmonoethylamine, andtrinonylamine. These may be used alone or as a mixture of two or morekinds thereof.

The total number of carbon atoms in groups bonded to one nitrogen atomis preferably from 3 to 24, more preferably from 5 to 24, still morepreferably from 5 to 10, and particularly preferably from 5 to 7.Further, as the group bonded to one nitrogen atom, an alkyl group, anaryl group, and an aryl-substituted alkyl group are preferred, and analkyl group is more preferred.

Among those, as the tertiary amine, triethylamine,N,N-dimethylisopropylamine, and trioctylamine are preferred, and fromthe viewpoints of easy availability and production cost, triethylamineand N,N-dimethylisopropylamine are more preferred.

By evaporating water from the reaction mixed solution after completionof the reaction, it is possible to acquire a mixture of 5% by mole orless of a bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphineammonium salt, 80% by mole or more of abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt, and 15% by mole or less of atris(6-methyl-3-sulphonatophenyl)phosphine triammonium salt, as a solid.This mixture will be hereinafter abbreviated as a mixture of ammoniumsalts.

In order to increase the content of thebis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt in the mixture of ammonium salts, column chromatography using amixed solvent including water, tetrahydrofuran, and the like as a mobilephase, which is passed through a column packed with silica gel, can beused. Alternatively, a method in which an aqueous solution of a mixtureof alkali metal salts is prepared and washed with an organic solventsuch as 2-butanone can also be used.

A palladium catalyst comprised of thebis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt obtained as above, or a mixture containing the same, and apalladium compound is excellent as a catalyst for a telomerizationreaction. Examples of the telomerization reaction include a reaction inwhich butadiene is reacted with water in the presence of a palladiumcatalyst, a tertiary amine, and carbon dioxide to obtain2,7-octadien-1-ol. In the telomerization reaction, the selectivity for2,7-octadien-1-ol is improved and the recovery of the palladium catalystis high, and therefore, the industrial availability is very high.

Furthermore, preferred examples of the palladium compound include0-valent palladium compounds such as bis(t-butylisonitrile)palladium(0), bis(t-amylisonitrile)palladium (0),bis(cyclohexylisonitrile)palladium (0), bis(phenylisonitrile)palladium(0), bis(p-tolylisonitrile)palladium (0),bis(2,6-dimethylphenylisonitrile)palladium (0),tris(dibenzylideneacetone) dipalladium (0), (1,5-cyclooctadiene)(maleicanhydride)palladium (0), bis(norbornene)(maleic anhydride)palladium (0),bis(maleic anhydride)(norbornene)palladium (0),(dibenzylideneacetone)(bipyridyl)palladium (0),(p-benzoquinone)(o-phenanthroline)palladium (0),tetrakis(triphenylphosphine)palladium (0),tris(triphenylphosphine)palladium (0), bis(tritolylphosphine)palladium(0), bis(trixylylphosphine)palladium (0),bis(trimesitylphosphine)palladium (0),bis(tritetramethylphenyl)palladium (0), andbis(trimethylmethoxyphenylphosphine)palladium (0); and divalentpalladium compounds such as palladium (II) chloride, palladium (II)nitrate, tetraammine dichloropalladium (II), disodiumtetrachloropalladium (II), palladium (II) acetate, palladium (II)benzoate, palladium (II) α-picolinate, bis(acetylacetone)palladium (II),bis(8-oxyquinoline)palladium (II), bis(allyl)palladium (II), (η-allyl)(η-cyclopentadienyl)palladium (II),(η-cyclopentadienyl)(1,5-cyclooctadiene)palladium (II)tetrafluoroborate, bis(benzonitrile)palladium (II) acetate,di-μ-chlorodichlorobis(triphenylphosphine)dipalladium (II),bis(tri-n-butylphosphine)palladium (II) acetate, and 2,2-bipyridylpalladium (II) acetate.

Furthermore, in the case where the telomerization reaction is carriedout industrially, a step of mixing the telomerization reaction liquidobtained in the telomerization reaction step with an organic solventhaving a dielectric constant of 2 to 18 at 25° C., followed byperforming phase separation in the presence of carbon dioxide, therebyobtaining 2,7-octadien-1-ol from an organic phase (product separationstep), and a step of recovering an aqueous phase including the palladiumcatalyst with high efficiency (catalyst recovery step) are preferablycarried out. At this time, in the case of using thebis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt or the mixture containing the same, of the present invention, as araw material for a palladium catalyst, the selectivity for a desiredproduct and the recovery of the palladium catalyst are higher, ascompared with other palladium catalysts, and therefore, the productioncost is reduced, which is thus preferable.

Furthermore, examples of the organic solvent having a dielectricconstant of 2 to 18 at 25° C. include n-dodecane, cyclohexane,1,4-dioxane, benzene, p-xylene, m-xylene, toluene, dibutyl ether,diisopropyl ether, propanenitrile, ethylphenyl ether, diethyl ether,methyl-t-butyl ether, cyclopentylmethyl ether, fluorobenzene,2-methyltetrahydrofuran, tetrahydrofuran, 2-heptanone,4-methyl-2-pentanone, cyclopentanone, 2-hexanone, 2-pentanone,cyclohexanone, 3-pentanone, and acetophenone. Further, the dielectricconstant of the organic solvent is preferably from 3 to 10.

EXAMPLES

Hereinafter, the present invention will be described in more detail withreference to Examples, but the present invention is not limited to suchExamples in any case.

Hereinafter, in the production of various water-solubletriarylphosphines, the production was carried out at room temperature,at normal pressure, or under a nitrogen atmosphere unless otherwisespecified, and as the solvent, those which had been purged with nitrogenin advance were used.

In addition, the water-soluble triarylphosphine obtained by sulphonatingtriarylphosphine is a mixture of those in which the number of sulphogroups introduced is 1 to 3, and may further include oxides formed byoxidation of the phosphorus.

The composition ratios (mass ratios) thereof in the water-solubletriarylphosphine were quantified from peak areas of ³¹P obtained bymeasurement using a nuclear magnetic resonance apparatus “AVANCE III 400USPlus” (manufactured by Bruker BioSpin K. K.) with adimethylsulphoxide-d₆ (hereinafter referred to as DMSO-d₆) solutionprepared such that the concentration of the produced water-solubletriarylphosphine is 0.05 mol/L. The chemical shift of ³¹P in this caseis a value at 305 K in the case where the chemical shift of the DMSO-d₆solution prepared to have a concentration of the phosphoric acid of 0.05mol/L is set to 0 ppm.

Furthermore, the structure of the water-soluble triarylphosphine isdetermined from the chemical shifts and the peak areas of ³¹P and ¹Hobtained by measurement using a nuclear magnetic resonance apparatus“AVANCE III 600 USPlus” (manufactured by Bruker BioSpin K. K.) with adeuterium oxide solution prepared to have a concentration of 10 mmol/L.The chemical shift of ³¹P in this case is a value at 300 K in the casewhere the chemical shift of a deuterium oxide solution prepared to havea concentration of the phosphoric acid of 10 mmol/L is set to 0 ppm. Thechemical shift of ¹H in this case is a value at 300 K in the case wherethe chemical shift of a deuterium oxide solution prepared to have aconcentration of trimethylsilylpropanoic acid-d₄ (hereinafterabbreviated as TSP) of 5 mmol/L is set to 0 ppm.

Sodium ions were quantified using an atomic absorption spectrophotometer“AA-7000F” (manufactured by Shimadzu Corporation).

For the operation for purifying a desired product, a high performanceliquid chromatographic system (manufactured by Nihon Waters K.K., DELTA600 MULTI-SOLVENT Systems, 2998 Photodiode Array Detector, ColumnHeater, Chromatography Data Software Empower 1) was used. Further, as areversed phase chromatography column, “TSKgel ODS-80Ts” (particlediameter of 5 μm, inner diameter of 20 mm, and length of 250 mm)manufactured by Tosoh Corporation, was used.

<Production of Water-Soluble Triarylphosphine>

Example 1

Production of Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine

A sulphonation reaction was carried out in a batch mode. A 50 Lglass-lined reactor equipped with a thermometer, a stirring device, anda jacket was used. 9.84 kg of concentrated sulphuric acid at aconcentration of 97.4% by mass was placed in the reactor and cooled to16° C. under stirring. Subsequently, 10.91 kg (35.84 mol) oftris(2-methylphenyl)phosphine (hereinafter abbreviated as TOTP) wasintroduced thereinto over 1 hour so as to maintain the temperature at30° C. or lower. Thereafter, 37.60 kg (131.50 mol in terms of sulphurtrioxide) of fuming sulphuric acid containing 28% by mass of sulphurtrioxide was added thereto over 3 hours, while controlling the liquidtemperature such that it was in a range of 30° C. to 40° C.Subsequently, the flow path of fuming sulphuric acid was washed with 1kg of concentrated sulphuric acid at a concentration of 97.4% by mass.The reaction was carried out at a liquid temperature of from 20° C. to30° C. over 4 hours.

On the other hand, 70 kg of ion-exchanged water was placed in a 200 Lglass-lined reactor equipped with a thermometer, a stirring device, anda jacket, and the total amount of the above sulphonation reaction liquidwas transferred thereto over 1 hour. Further, the flow path of thesulphonation reaction liquid was washed with 10 kg of ion-exchangedwater, and the resultant was added to the above diluted liquid. Inaddition, the liquid temperature was controlled such that it was in arange of 20° C. to 40° C., thereby acquiring 137.80 kg of a dilutedsulphonation reaction liquid.

27.50 kg (7.15 mol in terms of phosphorous atoms) of a dilutedsulphonation reaction liquid and 5 kg of ion-exchanged water were addedto a 200 L glass-lined reactor equipped with a thermometer, a stirringdevice, and a jacket. 24.10 kg of an aqueous 30.2%-by-mass sodiumhydroxide solution was supplied thereto over 3 hours while controllingthe liquid temperature such that it was in a range of 10° C. to 30° C.Further, 1.66 kg of an aqueous 4%-by-mass sodium hydroxide solution wasadded thereto over 1.7 hours. Thus, a neutralized liquid at pH 7.99 wasacquired.

The neutralized liquid was allowed to exist in the range of 80 kPa to100kPa at 35° C. to 65° C. and concentrated over 4.5 hours, and 37 kg ofwater was evaporated therefrom. 45 kg of methanol was added to theconcentrate, followed by stirring at 40° C. for 1 hour. Further, themixture was allowed to exist in the range of 4 kPa to 55 kPa at 40° C.to 55° C. and concentrated over 2.4 hours, and 45 kg of methanol wasevaporated therefrom. 147 kg of methanol was added to the concentrate,followed by stirring at 40° C. to 60° C. for 1 hour. Thereafter, themixture was cooled to 30° C. or lower.

The methanol solution was allowed to pass through a pressure filter madeof SUS304 in which 5 kg of “Celpure (registered trademark) S1000”manufactured by Advanced Minerals Corporation, as a high-puritydiatomite filter aid was placed, thereby acquiring a filtrate. Inaddition, the filter aid was washed with 30 kg of methanol and thefiltrate was combined with the above filtrate.

The total amount of the above acquired methanol solution was put into a100 L glass-lined reactor equipped with a thermometer, a stirringdevice, and a jacket, allowed to exist in the range of 4 kPa to 55 kPaat 40° C. to 55° C., and concentrated to dryness over 18 hours, therebyacquiring 3.56 kg of a white solid (hereinafter referred to as anacquisition 1).

The acquisition 1 was a mixture including 0.13 kg (0.33 mol) of abis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine sodium salt asa mono-form, 2.91 kg (5.72 mol) of abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine disodium saltas a di-form, and 0.52 kg (0.85 mol) of atris(6-methyl-3-sulphonatophenyl)phosphine trisodium salt as a tri-form.

From the viewpoint that 3.56 kg (6.90 mol in terms of phosphorous atoms)of the acquisition 1 could be acquired from 27.50 kg (7.15 mol in termsof phosphorous atoms) of a diluted sulphonation reaction liquid, theyield based on the phosphorous atoms ranging from the sulphonation stepto the neutralization step was 96.5%.

A column made of an acrylic resin (100 mm in diameter and 760 mm inheight), packed with 5 kg of a strongly acidic cation exchange resin“Dowex G-26”, was prepared. 12 kg of an aqueous solution including theacquisition 1 at 8.6% by mass (1044.0 g in terms of the acquisition 1,2023.4 mmol in terms of phosphorous atoms) was allowed to pass from theupper part of the column at a linear velocity of 9.3 m/hr to 12.5 m/hr.The obtained aqueous solution was concentrated to dryness in the rangeof 35° C. to 70° C. at 4 kPa to 55 kPa to obtain 914.5 g of a whitesolid (hereinafter referred to as an acquisition 2).

³¹P-NMR (400 MHz, 305 K, DMSO-d₆, phosphoric acid, ppm) δ:bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine as a mono-formshowed a peak at −28.72,bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine as a di-formshowed a peak at −26.00, and tris(6-methyl-3-sulphophenyl)phosphine as atri-form showed a peak at −18.85.

The acquisition 2 was a mixture containing 35.3 g (91.9 mmol, 4.73% bymole) of bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 749.4 g(1613.4 mmol, 83.01% by mole) ofbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, and 129.8 g(238.3 mmol, 12.26% by mole) of tris(6-methyl-3-sulphophenyl)phosphine.

According to the atomic absorption analysis of the acquisition 2, thesodium content included in the acquisition 2 was 23 ppm or less in termsof sodium atoms. From the viewpoint that the number of sulpho groupscontained in 1.0 kg of the acquisition 2 was 4410.6 mmol and the contentof the sodium atoms was 1.0 mmol, 99.98% by mole or more of thesulphonate groups had been converted to sulpho groups.

From the viewpoint that 914.5 g (1943.6 mmol in terms of phosphorousatoms) of an acquisition 2 could be acquired by using 1044.0 kg (2023.4mmol in terms of phosphorous atoms) of the acquisition 1, the yieldbased on the phosphorous atoms in the ion exchange step was 95.5%.

Example 2

Purification of Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine

Using a high performance liquid chromatographic system equipped with areversed phase chromatography column, a mixed liquid containing 70% bymass of water and 30% by mass of acetonitrile as a mobile phase waspassed through the system at 5.0 mL/minute in the state where a columnoven temperature was controlled to be 40° C.

1 g of an aqueous solution including 1% by mass of the acquisition 2 ofExample 1 was prepared, and injected. The photodiode array detector wasset to 275 nm and a distillate with a retention time of 17.5 minutes to20.0 minutes was recovered. This operation was repeated 10 times. Thecollected distillate was concentrated to dryness in the range of 35° C.to 70° C. and 4 kPa to 56 kPa to acquire 55.5 mg ofbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine as a white solid.

³¹P-NMR (400 MHz, 305 K, DMSO-d₆, phosphoric acid, ppm) δ: −26.00 (s)

³¹P-NMR (600 MHz, 300 K, deuterium oxide, phosphoric acid, ppm) δ:−24.69 (s)

¹H-NMR (600 MHz, 300 K, deuterium oxide, TSP, ppm) δ: 2.35 (s, 9 H),6.84 (t, 6.2 Hz, 1 H), 7.18 (t, 7.6 Hz, 1 H), 7.21 (dd, 2.8 Hz, 1.8 Hz,2 H), 7.35 (t, 6.3 Hz, 1 H), 7.41 (t, 7.4 Hz, 1 H), 7.45 (dd, 3.2 Hz,4.7 Hz, 2 H), 7.80 (dd, 6.1 Hz, 1.8 Hz, 2 H)

From the viewpoint that 55.5 mg (0.118 mmol in terms of phosphorousatoms) of a desired product could be acquired by using 100.0 mg (0.213mmol in terms of phosphorous atoms) of the acquisition 2, the yieldbased on the phosphorous atoms in the purification was 55.6%.

Example 3

Production of Bis (6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(triethylammonium) salt

500 g of an aqueous solution including 10% by mass of the acquisition 2of Example 1 was prepared. Further, this aqueous solution included 50.0g of the acquisition 2 with 106.3 mmol in terms of phosphorous atoms and221.4 mmol of sulpho groups. An aqueous solution of the acquisition 2was placed in a 3-neck flask having an inner capacity of 1 L, equippedwith a thermometer, a stirring device, a dropping funnel, and a nitrogengas line, and 24.6 g (243.5 mmol) of triethylamine was added theretothrough the dropping funnel, followed by stirring in the range of 20° C.to 30° C. over 1 hour, thereby performing a reaction.

Thereafter, the reaction liquid was concentrated to dryness in the rangeof 35° C. to 70° C. and 4 kPa to 56 kPa, thereby acquiring 68.2 g of awhite solid (hereinafter referred to as an acquisition 3).

³¹P-NMR (400 MHz, 305 K, DMSOd₆, phosphoric acid, ppm) δ: abis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphinetriethylammonium salt as a mono-form showed a peak at −28.12, abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(triethylammonium) salt as a di-form showed a peak at −25.00, and atris(6-methyl-3-sulphonatophenyl)phosphine tri(triethylammonium) salt asa tri-form showed a peak at −19.98.

The acquisition 3 was a mixture containing 2.3 g (4.7 mmol, 4.73% bymole) of a bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphinetriethylammonium salt, 55.5 g (83.2 mmol, 82.99% by mole) of abis(6-methyl-3-sulphonatoephenyl)(2-methylphenyl)phosphinedi(triethylammonium) salt, and 10.4 g (12.3 mmol, 12.28% by mole) of atris(6-methyl-3-sulphonatophenyl)phosphine tri(triethylammonium) salt.

From the viewpoint that 68.2 g (100.2 mmol in terms of phosphorousatoms) of the acquisition 3 could be acquired by using 50.0 g (106.3mmol in terms of phosphorous atoms) of the acquisition 2, the yieldbased on the phosphorous atoms in the ammonium salt forming step was94.3%.

Example 4

Purification ofBis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(triethylammonium) salt

100 g of an aqueous solution including 50% by mass of the acquisition 3of Example 3 was prepared. Further, the present aqueous solutionincluded 50.0 g of the acquisition 3 with 73.5 mmol in terms ofphosphorous atoms. An aqueous solution of the acquisition 3 was placedin a 3-neck flask having an inner capacity of 300 L, equipped with athermometer, a stirring device, a dropping funnel, and a nitrogen gasline. To an aqueous solution of the acquisition 3 was added 100 g of2-butanone, followed by stirring for 30 minutes, and the mixture wasleft to stand for 30 minutes, and an operation of removing a 2-butanonephase was repeated three times. By concentrating the obtained aqueousphase to dryness in the range of 35° C. to 70° C. and 4 kPa to 56 kPa,41.7 g of a white solid was acquired.

The acquisition was a mixture containing 0.5 g (1.0 mmol, 1.69% by mole)of a bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphinetriethylammonium salt, 34.1 g (51.2 mmol, 84.53% by mole) of a bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(triethylammonium) salt, and 7.1 g (8.3 mmol, 13.78% by mole) of atris(6-methyl-3-sulphonatophenyl)phosphine tri(triethylammonium) salt.

From the viewpoint that 41.7 g (60.5 mmol in terms of phosphorous atoms)of a desired product could be acquired by using 50.0 g (73.5 mmol interms of phosphorous atoms) of the acquisition 3, the yield based on thephosphorous atoms in the purification was 82.4%.

Example 5

Production of Bis (6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(tri-n-octylammonium) salt

By carrying out the same operation as in Example 3 except that 86.1 g(243.5 mmol) of tri-n-octylamine was used instead of triethylamine,123.0 g of a pale orange high-viscosity liquid was acquired.

³¹P-NMR (400 MHz, 305 K, DMSO-d₆, phosphoric acid, ppm) δ: abis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphinetri-n-octylammonium salt as a mono-form showed a peak at −28.60, abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(tri-n-octylammonium) salt as a di-form showed a peak at −25.00, and atris(6-methyl-3-sulphonatophenyl)phosphine tri(tri-n-octylammonium) saltas a tri-form showed a peak at −17.67.

The acquisition was a mixture containing 3.6 g (4.9 mmol, 4.80% by mole)of a bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphinetri-n-octylammonium salt, 99.2 g (84.6 mmol, 82.87% by mole) of abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(tri-n-octylammonium) salt, and 20.2 g (12.6 mmol, 12.33% by mole) ofa tris(6-methyl-3-sulphonatophenyl)phosphine tri(tri-n-octylammonium)salt.

From the viewpoint that 123.0 g (102.1 mmol in terms of phosphorousatoms) of a desired product could be acquired by using 50.0 g (106.3mmol in terms of phosphorous atoms) of the acquisition 2, the yieldbased on the phosphorous atoms in the ammonium salt forming step was96.0%.

Example 6

Production of Bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(dimethylisopropylammonium) salt

By carrying out the same operation as in Example 3 except that 21.2 g(243.5 mmol) of N,N-dimethylisopropylamine was used instead oftriethylamine, 67.5 g of a white solid was acquired.

³¹P-NMR (400 MHz, 305 K, DMSO-d₆, phosphoric acid, ppm) δ: abis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphinedimethylisopropylammonium salt as a mono-form showed a peak at −28.17, abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(dimethylisopropylammonium) salt as a di-form showed a peak at −25.25,and a tris(6-methyl-3-sulphonatophenyl)phosphinetri(dimethylisopropylammonium) salt as a tri-form showed a peak at−21.50.

The acquisition was a mixture containing 2.4 g (5.0 mmol, 4.81% by mole)of a bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphinedimethylisopropylammonium salt, 54.8 g (85.9 mmol, 82.85% by mole) of abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinedi(dimethylisopropylammonium) salt, and 10.3 g (12.8 mmol, 12.34% bymole) of a tris(6-methyl-3-sulphonatophenyl)phosphinetri(dimethylisopropylammonium) salt.

From the viewpoint that 67.5 g (103.6 mmol in terms of phosphorousatoms) of a desired product could be acquired by using 50.0 g (106.3mmol in terms of phosphorous atoms) of the acquisition 2, the yieldbased on the phosphorous atoms in the ammonium salt forming step was97.5%.

<Telomerization Reaction>

Hereinafter, it is shown that the water-soluble triarylphosphine of thepresent invention is useful for a telomerization reaction with referenceto Reference Examples. Further, the present invention is not limited tosuch Reference Examples in any case.

Moreover, the concentrations of the palladium compounds and thephosphorus compounds included in the aqueous phase acquired by anextraction operation were quantified by subjecting a wet decompositionproduct to analysis using a polarized Zeeman atomic absorptionspectrophotometer “Z-5300 Type” (manufactured by Hitachi, Ltd.).

In addition, organic materials such as a tertiary amine and2,7-octadien-1-ol included in the telomerization reaction liquid or theaqueous phase including the palladium catalyst were analyzed andquantified by gas chromatography under the following measurementconditions.

(Analysis Conditions for Gas Chromatography)

Apparatus: GC-14 A (manufactured by Shimadzu Corporation)

Column used: G-300 (1.2 mm in internal diameter×20 m in length, and afilm thickness of 2 μm),

(Materials) manufactured by Chemicals Evaluation, and ResearchInstitute, Japan

Analysis conditions: an inlet temperature of 220° C. and a detectortemperature of 220° C.

Sample injection amount: 0.4 μL

Carrier gas: helium (260 kPa) is flowed at 10 mL/minute.

Column temperature: maintained at 60° C. for 5 minutes→raised at 10°C./minute→maintained at 220° C. for 9 minutes

Detector: hydrogen flame ionization detector (FID)

Reference Example 1

The telomerization reaction was carried out in a batch mode. A 3 Lautoclave equipped with a SUS316 electromagnetic induction stirringdevice including a 96 mL pressure container made of glass, for pumping apalladium catalyst, a 96 mL pressure container made of glass, forpumping a solvent, and a sampling port was used as a reactor. Further,the reaction was carried out at a stirring rotation speed of 500 rpm,and from the viewpoint that the reaction results at this time were notdifferent from those at 1,000 rpm, a sufficient stirring state could beachieved.

17.69 g of a tetrahydrofuran solution including 94.74 mg (0.422 mmol interms of palladium atoms) of palladium (II) acetate, and then 21.46 g ofan aqueous solution including 1.440 g (2.116 mmol in terms of trivalentphosphorous atoms) of the phosphorous compound obtained in Example 3were introduced into a pressure container made of glass and stirred for60 minutes to prepare a palladium catalyst liquid.

30.06 g of distilled water, 80.10 g of triethylamine, 97.50 g of2,7-octadien-1-ol, and 114.95 g (2.13 mol) of butadiene were put intothe autoclave, followed by stirring at 500 rpm in a closed system andwarming to 70° C. Thereafter, the palladium catalyst liquid was pumpedfrom the pressure container made of glass through carbon dioxide within10 seconds, while the total pressure was set to 1.2 MPa (gaugepressure). Further, a time point at which pumping of the palladiumcatalyst liquid was completed was defined as 0 hours at initiation ofreaction.

In addition, the ratio of the trivalent phosphorus atoms to thepalladium atoms at a time of preparation of a catalyst was 5.01, and inthe telomerization reaction, the amount of the palladium atoms withrespect to 1 mol of butadiene was 0.198 mmol, the mass ratio oftriethylamine to water was 1.55, and the mass ratio of a mixture ofbutadiene and 2,7-octadien-1-ol to water was 4.12.

For the telomerization reaction liquid after a predetermined reactiontime, the product was quantified by gas chromatography analysis.

The conversion of the butadiene was calculated by the followingEquation 1. Further, the respective units in the equations are mol.

Butadiene conversion (%)=100×{1−(Amount of butadiene in reaction liquid/Amount of butadiene introduced)}  [Equation 1]

Examples of the respective products include 2,7-octadien-1-ol,1,7-octadien-3-ol, 1,3,6-octatriene, 1,3,7-octatriene, 2,4,6-octatriene,and 4-vinylcyclohexene. However, 1,3,6-octatriene, 1,3,7-octatriene, and2,4,6-octatriene are collectively referred to as octatrienes. Theselectivities of the respective products were calculated by thefollowing Equation 2. Further, the respective units in the equations aremol.

Selectivity for each product (%)=50×(Amount of each product in reactionliquid/Amount of butadiene reacted)  [Equation 2]

The selectivities for high-boiling-point products which could not besufficiently quantified by gas chromatography were calculated by thefollowing Equation 3. Further, the respective units in the equations aremol.

Selectivity for high-boiling-point product (%)=100−(Total sum ofselectivities of the respective products, calculated by Equation2)  [Equation 3]

After 8 hours of the reaction, the butadiene conversion was 81.6%, theselectivity for 2,7-octadien-1-ol was 92.5%, the selectivity for1,7-octadien-3-ol was 3.2%, the selectivity for octatrienes was 2.6%,and the selectivity for the high-boiling-point products was 1.7%.Further, the selectivity for 4-vinylcyclohexene was 0.01% or less.

The autoclave was cooled to 25° C., and a reactionconsumption-equivalent amount of water and 330.23 g (a volume at 25° C.of 463.2 mL) of diethyl ether were pumped through carbon dioxide, usinga 96 mL pressure container made of glass, for pumping a solvent. Themixture was stirred for 1 hour while being pressurized to a totalpressure of 3 MPa (gauge pressure) with carbon dioxide. This mixedliquid was transferred to a pressure container equipped with a glasswindow, which had been pressurized to 3 MPa (gauge pressure) with carbondioxide using a pump, to carry out phase separation. The aqueous phasewas suitably recovered into a pressure container made of glass, whichhad been pressurized to 1 MPa (gauge pressure) with carbon dioxide,connected to a pressure container equipped with a glass window. Thepressure container made of glass was taken out, separated, and opened atnormal pressure, and the weight of the aqueous phase was measured, whilethe acquired aqueous phase was used for various types of analysis.

In addition, the mass ratio of diethyl ether to the telomerizationreaction liquid was 0.84.

The content of palladium included in the aqueous phase was calculatedfrom the concentration of palladium as demonstrated by the analysis witha polarized Zeeman atomic absorption spectrophotometer using a wetdecomposition product of the aqueous phase and the weight of therecovered aqueous phase. The recovery of the palladium atoms wascalculated by the following Equation 4. Further, the units of therespective amounts in the equations are mol.

Recovery of palladium atoms (%)=(Amount of palladium in aqueousphase/Amount of palladium introduced)×100  [Equation 4]

The content of phosphorous included in the aqueous phase was calculatedfrom the concentration of phosphorous as demonstrated by the analysiswith a polarized Zeeman atomic absorption spectrophotometer using a wetdecomposition product of the aqueous phase and the weight of therecovered aqueous phase. The recovery of the water-solubletriarylphosphine was calculated by the following Equation 5. Further,the units of the respective amounts in the equations are mol.

Recovery of water-soluble triarylphosphine (%)=100×(Amount ofphosphorous atoms in aqueous phase/Amount of phosphorous atomsintroduced)  [Equation 5]

The tertiary amine included in the aqueous phase was quantified byanalyzing the aqueous phase using gas chromatography. The recovery ofthe tertiary amine was calculated by the following Equation 6. Further,the units of the respective amounts in the equations are mol.

Recovery of tertiary amine (%)=100×(Amount of tertiary amine in aqueousphase/Amount of tertiary amine introduced)  [Equation 6]

The recovery of the palladium atoms into the aqueous phase was 87.6%,the recovery of phosphorous atoms was 80.7%, and the recovery oftriethylamine was 70.1%. Further, the amount of diethyl etherincorporated into the aqueous phase was 0.1% by mass or less.

Reference Example 2

The same operation as in Reference Example 1 except that 1.457 g (2.115mmol in terms of trivalent phosphorous atoms) of the phosphorouscompound obtained in Example 4 was used instead of the phosphorouscompound obtained in Example 3 was carried out. Further, the ratio ofthe trivalent phosphorous atoms to the palladium atoms at a time ofpreparation of the catalyst was 5.01.

After 8 hours of the reaction, the butadiene conversion was 80.2%, theselectivity for 2,7-octadien-1-ol was 92.7%, the selectivity for1,7-octadien-3-ol was 3.1%, the selectivity for octatrienes was 2.5%,and the selectivity for the high-boiling-point products was 1.7%.Further, the selectivity for 4-vinylcyclohexene was 0.01% or less.

The recovery of the palladium atoms into the aqueous phase was 88.9%,the recovery of phosphorous atoms was 84.6%, and the recovery oftriethylamine was 70.8%. Further, the amount of diethyl etherincorporated into the aqueous phase was 0.1% by mass or less.

Reference Example 3

The same operation as in Reference Example 1 except that 2.545 g (2.113mmol in terms of trivalent phosphorous atoms) of the phosphorouscompound obtained in Example 5 was used instead of the phosphorouscompound obtained in Example 3 was carried out. Further, the ratio ofthe trivalent phosphorous atoms to the palladium atoms at a time ofpreparation of the catalyst was 5.01.

After 6 hours of the reaction, the butadiene conversion was 74.4%, theselectivity for 2,7-octadien-1-ol was 93.1%, the selectivity for1,7-octadien-3-ol was 3.1%, the selectivity for octatrienes was 2.7%,and the selectivity for the high-boiling-point products was 1.1%.Further, the selectivity for 4-vinylcyclohexene was 0.01% or less.

The recovery of the palladium atoms into the aqueous phase was 86.9%,the recovery of phosphorous atoms was 76.8%, and the recovery oftriethylamine was 76.9%. Further, the amount of diethyl etherincorporated into the aqueous phase was 0.1% by mass or less.

Reference Example 4 Comparative

The same operation as in Reference Example 1 except that 2.120 g (2.120mmol in terms of trivalent phosphorous atoms) of adiphenyl(3-sulphonatophenyl)phosphine triethylammonium salt (with aprovision that it included 4.40% by mole of oxides) was used instead ofthe phosphorous compound obtained in Example 3 was carried out. Further,the ratio of the trivalent phosphorous atoms to the palladium atoms at atime of preparation of the catalyst was 5.02.

After 4 hours of the reaction, the butadiene conversion was 77.6%, theselectivity for 2,7-octadien-1-ol was 88.2%, the selectivity for1,7-octadien-3-ol was 5.1%, the selectivity for octatrienes was 5.1%,and the selectivity for the high-boiling-point products was 1.6%.Further, the selectivity for 4-vinylcyclohexene was 0.01% or less.

The recovery of the palladium atoms into the aqueous phase was 28.2%,the recovery of phosphorous atoms was 48.8%, and the recovery oftriethylamine was 65.5%. Further, the amount of diethyl etherincorporated into the aqueous phase was 0.1% by mass or less.

Reference Example 5 Comparative

The same operation as in Reference Example 1 except that 1.015 g (2.113mmol in terms of trivalent phosphorous atoms) of adiphenyl(6-methyl-3-sulphonatophenyl)phosphine triethylammonium salt(with a provision that it included it included 4.58% by mole of oxides)was used instead of the phosphorous compound obtained in Example 3 wascarried out. Further, the ratio of the trivalent phosphorous atoms tothe palladium atoms at a time of preparation of the catalyst was 5.01.

After 4 hours of the reaction, the butadiene conversion was 85.0%, theselectivity for 2,7-octadien-1-ol was 88.8%, the selectivity for1,7-octadien-3-ol was 5.0%, the selectivity for octatrienes was 4.4%,and the selectivity for the high-boiling-point products was 1.8%.Further, the selectivity for 4-vinylcyclohexene was 0.01% or less.

The recovery of the palladium atoms into the aqueous phase was 12.0%,the recovery of phosphorous atoms was 28.3%, and the recovery oftriethylamine was 76.5%. Further, the amount of diethyl etherincorporated into the aqueous phase was 0.1% by mass or less.

According to Example 1, it is apparent that a mixture of 5% by mole orless of bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% bymole or more of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine,and 15% by mole or less of tris(6-methyl-3-sulphophenyl)phosphine can beacquired with high yield.

Furthermore, according to Example 2, it is apparent thatbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine can be isolatedand purified by column chromatography.

According to Examples 3, 5, and 6, it is apparent that abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt can be acquired with high yield by reactingbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine with a tertiaryamine having a total of 3 to 27 carbon atoms in groups bonded to onenitrogen atom.

According to Example 4, it is apparent that thebis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt can be made to have increased purity by washing with a ketonesolvent or the like.

According to Reference Examples 1 to 5, it is apparent that thebis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt provided by the present invention can be obtained with higherselectivity in the telomerization reaction and the recovery of thepalladium catalyst is higher, as compared with other water-solubletriarylphosphines, and therefore, it is useful when carrying outindustrial telomerization reactions.

INDUSTRIAL APPLICABILITY

The bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt obtained by usingbis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of the presentinvention is useful for a telomerization reaction of two molecules of analkadiene such as butadiene with a nucleophilic reactant such as water.

2. A bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphinediammonium salt obtained by reacting thebis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of claim 1 with atertiary amine having a total of 3 to 27 carbon atoms in groups bondedto one nitrogen atom.
 3. Thebis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt of claim 2, wherein the tertiary amine is trimethylamine,triethylamine, tripropylamine, triisopropylamine, tributylamine,triisobutylamine, tri-s-butylamine, tri-t-butylamine, tripentylamine,triisopentylamine, trineopentylamine, trihexylamine, triheptylamine,trioctylamine, triphenylamine, tribenzylamine, N,N-dimethylethylamine,N,N-dimethylpropylamine, N,N-dimethylisopropylamine,N,N-dimethylbutylamine, N,N-dimethylisobutylamine,N,N-dimethyl-s-butylamine, N,N-dimethyl-t-butylamine,N,N-dimethylpentylamine, N,N-dimethylisopentylamine,N,N-dimethylneopentylamine, N,N-dimethylhexylamine,N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine,N,N-dimethyldecylamine, N,N-dimethylundecylamine,N,N-dimethyldodecylamine, N,N-dimethylphenylamine,N,N-dimethylbenzylamine, N,N-diethylmonomethylamine,N,N-dipropylmonomethylamine, N,N-diisopropylmonomethylamine,N,N-dibutylmonomethylamine, N,N-diisobutylmonomethylamine,N,N-di-s-butylmonomethylamine, N,N-di-t-butylmonomethylamine,N,N-dipentylmonomethylamine, N,N-diisopentylmonomethylamine,N,N-dineopentylmonomethylamine, N,N-dihexylmonomethylamine,N,N-diheptylmonomethylamine, N,N-dioctylmonomethylamine,N,N-dinonylmonomethylamine, N,N-didecylmonomethylamine,N,N-diundecylmonomethylamine, N,N-didodecylmonomethylamine,N,N-diphenylmonomethylamine, N,N-dibenzylmonomethylamine,N,N-dipropylmonomethylamine, N,N-diisopropylmonoethylamine,N,N-dibutylmonoethylamine, N,N-diisobutylmonoethylamine,N,N-di-s-butylmonoethylamine, N,N-di-t-butylmonoethylamine,N,N-dipentylmonoethylamine, N,N-diisopentylmonoethylamine,N,N-dineopentylmonoethylamine, N,N-dihexylmonoethylamine,N,N-diheptylmonoethylamine, N,N-dioctylmonoethylamine,N,N-dinonylmonoethylamine, N,N-didecylmonoethylamine,N,N-diundecylmonoethylamine, N,N-didodecylmonoethylamine,N,N-diphenylmonoethylamine, N,N-dibenzylmonoethylamine, andtrinonylamine.
 4. A mixture, comprising: 5% by mole or less ofbis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% by mole ormore of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, and 15%by mole or less of tris(6-methyl-3-sulphophenyl)phosphine.
 5. A mixture,comprising: 80% by mole or more of abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt obtained by reacting the mixture of claim 4 with a tertiary aminehaving a total of 3 to 27 carbon atoms in groups bonded to one nitrogenatom.
 6. A method for producing thebis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of claim 1,comprising: reacting 2.5 moles to 4.5 moles of sulphur trioxide with 1mole of tris(2-methylphenyl)phosphine in the presence of concentratedsulphuric acid, thereby producing a sulphonation reaction liquid, anddiluting the obtained sulphonation reaction liquid with water, therebyproducing a diluted liquid; neutralizing the diluted liquid with analkali metal hydroxide, thereby producing an aqueous solution; andbringing the aqueous solution into contact with a strongly acidic cationexchange resin.
 7. A method for producing abis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine diammoniumsalt. the method comprising: reacting thebis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of claim 1 with atertiary amine having a total of 3 to 27 carbon atoms in groups bondedto one nitrogen atom.